CN107512906A - A kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof - Google Patents
A kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof Download PDFInfo
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- 239000003989 dielectric material Substances 0.000 title claims abstract description 37
- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 229910010252 TiO3 Inorganic materials 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002019 doping agent Substances 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 229910002976 CaZrO3 Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 229910002113 barium titanate Inorganic materials 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 description 13
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The invention discloses a kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof.The molecular formula of compound of the present invention is 0.90BaTiO3‑0.10Bi0.5A0.5TiO3, wherein, A is Na or K.The anti-reduction X9R type ceramic capacitor dielectric materials of the present invention, it includes compound and secondary doping agent；Secondary doping agent includes MnO2, component A and B component；Component A is Nb2O5And/or Ta2O5；B component is CeO2、CaZrO3At least one of with MgO；The mass ratio of secondary doping agent and compound is 0.5~2.0:100.Its preparation method, comprises the following steps：By compound and secondary doping agent mixing and ball milling, drying, sieving, ceramic powder is obtained；After ceramic powder tabletting, sintered in reducing atmosphere stove, that is, obtain anti-reduction X9R type ceramic capacitor dielectric materials.Present media material temperature stability is good, and (Δ C/C25)≤± 15% can be met in wider temperature range (55~200 DEG C), and dielectric constant is high, good reliability；Its preparation method is simple, and cost is cheap, and environmental sound.
Description
Technical field
The present invention relates to a kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof, belong to electronics member device
The technical field of ceramic material of part.
Background technology
Multilayer ceramic capacitor (Multilayer Ceramic Capacitor, abbreviation MLCC), due to high capacitance,
Small size, low cost, high reliability and excellent high frequency characteristics, are widely used in the fields such as electronics, communication, Aero-Space,
It is one of current most popular passive electronic components.
According to International Electronics Industry Association (Electronic Industries Association, EIA) EIA standards,
X9R types capacitor is on the basis of 25 DEG C of capacitance, in the range of -55~200 DEG C, rate of change of capacitance (Δ C/C25)≤±
15%.In fields such as automobile, oil drilling, Aero-Space, military projects, involved all kinds of electronic components needs bear higher
Operating temperature.For example, high-power phased-array radar, armored vehicle, missile-borne/arrow carry circuit, the engine system of aerospace equipment
Electronic equipment of oil and gas reserves etc. is united and seeks, the hot operation temperature that its extreme harsh working environment is required to MLCC is prolonged
More than 150 DEG C are reached, or even to reach more than 200 DEG C.Obvious X7R and X8R types capacitor can not meet actual demand, he
Use temperature upper limit be respectively 125 DEG C and 150 DEG C.Therefore, higher temperature stable type X9R type condenser dielectric materials are researched and developed
Material, has very important actual application value.
Noble metal is gradually instead of to reduce the base-metal inner-electrode such as MLCC production costs, Ni, Cu.And base metal is in air
When being sintered under atmosphere, it is easy to be oxidized and be easy to ceramic material and react, deteriorate conductive capability, lose the work of interior electrode
With.Therefore base-metal inner-electrode MLCC must be sintered under reducing atmosphere, but now necessarily require dielectric substance in also Primordial Qi
Do not turn into semiconductor under being sintered under atmosphere, and there are sufficiently high insulaion resistance and excellent dielectric properties.
At present, Large Copacity temperature-stable MLCC dielectric materials are mainly by barium titanate (BaTiO3) composition.BaTiO3It is a kind of
Ferroelectric material, there is typical ABO3Perovskite structure, there is very high dielectric constant at room temperature, 2000~4000 can be reached,
It is highly suitable as dielectric material.But higher than after Curie temperature (about 120~130 DEG C), dielectric constant can drastically decline, sternly
Ghost image rings MLCC temperature stability, limits application under the high temperature conditions.
The content of the invention
It is an object of the invention to provide a kind of anti-reduction X9R type ceramic capacitor dielectric materials and preparation method thereof, this hair
Bright dielectric material temperature stability is good, can meet in the wider temperature range (- 55~200 DEG C) (Δ C/C25)≤±
15%, and dielectric constant is high, good reliability；Its preparation method is simple, and cost is cheap, and environmental sound.
Compound provided by the invention, its molecular formula are 0.90BaTiO3-0.10Bi0.5A0.5TiO3, wherein, A is Na or K.
Present invention also offers the preparation method of above-mentioned compound, comprise the following steps：(1) by Bi2O3、A2CO3With
TiO2After mixing and ball milling, drying, sieving and pre-burning, Bi is obtained0.5A0.5TiO3Powder；
(2) by the Bi0.5A0.5TiO3Powder and BaTiO3After mixing and ball milling, drying, sieving and pre-burning, that is, obtain described
Compound.
In above-mentioned method, the Bi2O3, the A2CO3With the TiO2Mol ratio be 1：1：4；
The Bi0.5A0.5TiO3Powder and the BaTiO3Mol ratio be 1：9.
In above-mentioned method, in the step (1), the medium of the ball milling is selected from ethanol and/or isopropanol, the ball milling
Time can be 16~24h, concretely 24h or 20~24h；The temperature of the drying is 60~80 DEG C, concretely 70 DEG C
Or 65~75 DEG C, the time of the drying is 8~12h, concretely 12h or 10~12h；The screen number of the sieving is 60
~120 mesh, concretely 100 mesh or 70~110 mesh；The temperature of the pre-burning be 850~950 DEG C, concretely 900 DEG C or
880~930 DEG C, the time of the pre-burning is 1~3h, concretely 3h or 1.5~3h；
In the step (2), the average grain diameter of the barium titanate can be 10~100nm, concretely 50nm, 20~80nm
Or 30~100nm；The medium of the ball milling is deionized water, and the time of the ball milling can be 16~24h, concretely 24h or
20~24h；The temperature of the drying can be 100~120 DEG C, concretely 100 DEG C or 100~110 DEG C, the time of the drying
For 8~12h, concretely 12h or 10~12h；The screen number of the sieving can be 60~120 mesh, concretely 100 mesh or
80~110 mesh；The temperature of the pre-burning can be 950~1100 DEG C, concretely 1050 DEG C, 1000~1050 DEG C or 1000~
1100 DEG C, the time of the pre-burning can be 2~8h, concretely 8h, 6~8h or 3~8h.
Present invention also offers a kind of anti-reduction X9R type ceramic capacitor dielectric materials, it includes above-mentioned compound and two
Secondary dopant；
The secondary doping agent includes MnO2, component A and B component；The component A is Nb2O5And/or Ta2O5；The B groups
It is divided into CeO2、CaZrO3At least one of with MgO；
The mass ratio of the secondary doping agent and the compound is 0.5~2.0:100.
In above-mentioned dielectric material, the MnO2Mass ratio with the compound can be 0.1~1.0：100；
The component A and the mol ratio of the compound can be 1.0~4.0：100；
The mass ratio of the B component and the compound can be 0.5~2.0：100.
The present invention, the anti-reduction X9R types ceramic capacitor dielectric material are made up of the compound and secondary doping agent.
In the present invention, the secondary doping agent is by MnO2、Nb2O5And CaZrO3Composition；
The concrete component content of the anti-reduction X9R type ceramic capacitor dielectric materials is as follows：The MnO2With it is described
0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mass ratio can be 0.3:99.7、0.4:99.6、0.5:99.5th, 0.3~0.6：100
Or 0.1~0.6：100；
The Nb2O5With the 0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mol ratio can be 2.0：98.0 or 1.0~
3.0：100；
The CaZrO3With the 0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mass ratio can be 1.0:99.0 or 0.1~
1.5：100.
Invention further provides the preparation method of above-mentioned dielectric material, comprise the following steps：By the compound
With the secondary doping agent mixing and ball milling, drying, sieving, ceramic powder is obtained；After the ceramic powder tabletting,
Sintered in reducing atmosphere stove, that is, obtain the anti-reduction X9R type ceramic capacitor dielectric materials.
In above-mentioned preparation method, the reducing atmosphere of the reducing atmosphere stove is N2/H2；
The process of the sintering comprises the following steps：
1) 300~400 DEG C are risen to 150~200 DEG C/h heating rate, is incubated 0.5~2h；
2) in the reducing atmosphere, humidify simultaneously, partial pressure of oxygen is controlled 10-9~10-13In atm, with 150~200
DEG C/temperature rises to 1150~1200 DEG C and is sintered, and be incubated 1~3 hour by h heating rate；
3) partial pressure of oxygen is controlled 10-4~10-5Atm anneals, and is cooled the temperature to 200~300 DEG C/h rate of temperature fall
800~1100 DEG C, 2.5~4h is incubated, room temperature is cooled to the reducing atmosphere stove.
In the present invention, room temperature refers to 10~30 DEG C.
In above-mentioned preparation method, the medium of the ball milling is deionized water, and the time of the ball milling can be 16~24h,
Concretely 24h；
The temperature of the drying can be 100~120 DEG C, concretely 100 DEG C or 100~115 DEG C, the time of the drying
Can be 6~12h, concretely 12h or 8~12h；
The screen number of the sieving can be 60~120 mesh, concretely 100 mesh, 80~110 mesh or 70~120 mesh.
In above-mentioned preparation method, the tableting processes are that the ceramic powder is mixed into pressure with organic binder bond
Piece；
The mass ratio of the ceramic powder and the organic binder bond is 100：1.5~3.0.
In the present invention, the organic binder bond is binding agent commonly used in the art, and concretely mass percentage concentration is 5%
PVOH (PVA) solution and/or polyvinyl acetal (PVB) solution；
The method of the tabletting is carried out according to this area conventional method.
The present invention has advantages below：
Anti- reduction X9R type ceramic capacitor dielectric materials provided by the invention, temperature stability is good, can be in wider temperature
Spend and meet (Δ C/C25)≤± 15% in scope (- 55~200 DEG C), and dielectric constant is high, good reliability.The present invention is significantly
The Curie temperature of the anti-reduction ceramic capacitor dielectric material of X9R types is improved, has widened its temperature use range, it is held temperature
Rate of change disclosure satisfy that EIA X9R standards；Dielectric material room temperature dielectric constant ＞ 2000, room temperature loss ＜ 2%, room temperature resistance
Rate ＞ 1012Ω·cm.Using the formula and technique of the present invention, the X9R type reduction-resistant ceramic dielectric materials of function admirable can be obtained
Material, sintering temperature is relatively low, and technique is simple, and cost is cheap, and environmental sound.The anti-reduction X9R type ceramic medium materials of the present invention
Have broad application prospects, and domestic research in this respect at present is still far from perfect, and is also not carried out scale industrialization.
Anti- reduction X9R type ceramic capacitor dielectric materials provided by the present invention and preparation method thereof, have good application prospect and
Industrialization prospect.
Brief description of the drawings
Fig. 1 is the dielectric constant with temperature changing rule of 1~sample of ceramic capacitor dielectric material sample 3 in embodiment 1.
Fig. 2 is that the temperature coefficient of capacitance of 1~sample of ceramic capacitor dielectric material sample 3 in embodiment 1 varies with temperature rule
Rule.
Fig. 3 is the SEM photograph of ceramic capacitor dielectric material sample 1 in embodiment 1.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
The preparation of the anti-reduction ceramic capacitor dielectric material of embodiment 1, X9R types and performance detection
By the pure Bi of chemistry2O3、Na2CO3And TiO2According to mol ratio 1:1:4 ratio carries out weighing mixing, using ethanol as
Ball-milling medium (presses 1g total raw materials：10ml ethanol), ball milling 24h, 12h is dried in 70 DEG C of air dry oven, with 100 mesh sieve
Cross and be sieved to crucible, pre-burning 3h obtains Bi at 900 DEG C0.5Na0.5TiO3(Chinese：Bismuth-sodium titanate) powder；
By the BaTiO that average grain diameter is 50nm3(Chinese：Barium titanate) with obtained bismuth-sodium titanate powder according to mole
Than 9:1 ratio weighs mixing, using deionized water as medium ball milling 24h, 12h is dried in 100 DEG C of air dry oven, with 100
Mesh sieve, which is crossed, is sieved to crucible, and pre-burning 8h obtains barium titanate-bismuth-sodium titanate (0.90BaTiO at 1050 DEG C3-
0.10Bi0.5A0.5TiO3) compound.
By the 0.90BaTiO of gained3-0.10Bi0.5Na0.5TiO3Compound is mixed with secondary doping agent.Secondary doping
Agent is by MnO2、Nb2O5And CaZrO3Composition, wherein MnO2With 0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mass ratio be followed successively by
0.3:99.7、0.4:99.6、0.5:99.5 Nb2O5With 0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mol ratio be 2.0：
98.0 CaZrO3With 0.90BaTiO3-0.10Bi0.5Na0.5TiO3Mass ratio be 1.0:99.0.Mix according to the above ratio, to go
Ionized water is ball-milling medium ball milling 24h, and 12h is dried in 100 DEG C of air dry oven, is sieved with 100 mesh sieve, obtains ceramics
Material powder.It is 5% polyvinyl acetal (PVB) solution for organic binder bond using mass percentage concentration, to ceramic material
Organic binder bond is added in powder to be granulated, and a diameter of 10mm, thickness 1mm disc-shaped green compact are depressed in 2Mpa pressure.
It is sintered in reducing atmosphere stove, 400 DEG C of dumping 2h is raised to 200 DEG C/h heating rate in atmosphere furnace；Connect
And temperature is raised to 1150 DEG C with same heating rate be sintered, be incubated 3 hours, should during need to be passed through N2/H2, together
When humidify, by partial pressure of oxygen control 10-12atm；Annealed under the conditions of weak oxide, Control for Kiln Temperature is incubated 2.5h, oxygen at 1050 DEG C
Partial pressure is controlled 10-4In the range of atm；Room temperature (20~30 DEG C) is cooled to the furnace after the completion of last sintering procedure, that is, obtains anti-go back
Former X9R types ceramic capacitor dielectric material.
Anti- reduction X9R type ceramic capacitor dielectric materials obtained above are according to MnO2With 0.90BaTiO3-
0.10Bi0.5Na0.5TiO3Mass ratio be followed successively by 0.3:99.7、0.4:99.6、0.5:99.5 are respectively labeled as sample 1,2 and 3,
As shown in table 1.
Upper silver electrode is burnt into the above-mentioned ceramic disks sample both sides sintered, wafer capacitance device is made, then tests and counts
The relative dielectric constant of ceramics sample, loss angle tangent, temperature coefficient of capacitance, insulation resistivity.Gained sample 1-3 is normal with respect to dielectric
Number, rate of change of capacitance variation with temperature, as shown in Fig. 1 and accompanying drawing 2.From Fig. 1 and Fig. 2, the present invention adulterates appropriate MnO2、
Nb2O5And CaZrO30.90BaTiO afterwards3-0.10Bi0.5Na0.5TiO3Composite ceramic material, have within the scope of very wide temperature
Stable temperature characterisitic, meets X9R standards, i.e., rate of change of capacitance meet in the range of -55~200 DEG C (Δ C/C25)≤±
15%, it may be used as the anti-reduction ceramic capacitor dielectric material of X9R types.Electrical performance testing result is as shown in table 2, can by table 2
Know, meet the anti-reduction 0.90BaTiO of X9R characteristic requirements3-0.10Bi0.5Na0.5TiO3Composite ceramics has preferably insulation special
Property and relatively low room temperature loss.Fig. 3 is the microstructure photo of sample 1, from the figure 3, it may be seen that meeting the anti-reduction of X9R characteristic requirements
0.90BaTiO3-0.10Bi0.5Na0.5TiO3Composite ceramics densified sintering product, averagely about 0.5 μm of crystallite dimension.
Each component accounts for the addition of total amount in table 1, ceramic capacitor dielectric material sample 1-3
Total amount refers to concrete component and compound 0.90BaTiO in secondary doping agent3-0.10Bi0.5A0.5TiO3Quality
Summation.
The electric performance test result of table 2, ceramic capacitor dielectric material sample 1-3
Claims (10)
- A kind of 1. compound, it is characterised in that：The molecular formula of the compound is 0.90BaTiO3-0.10Bi0.5A0.5TiO3, its In, A is Na or K.
- 2. the preparation method of the compound described in claim 1, comprises the following steps：(1) by Bi2O3、A2CO3And TiO2Mix ball After mill, drying, sieving and pre-burning, Bi is obtained0.5A0.5TiO3Powder；(2) by the Bi0.5A0.5TiO3Powder and BaTiO3After mixing and ball milling, drying, sieving and pre-burning, that is, obtain described compound Thing.
- 3. according to the method for claim 2, it is characterised in that：The Bi2O3, the A2CO3With the TiO2Mol ratio For 1：1：4；The Bi0.5A0.5TiO3Powder and the BaTiO3Mol ratio be 1：9.
- 4. according to the method in claim 2 or 3, it is characterised in that：In the step (1), the medium of the ball milling is selected from Ethanol and/or isopropanol, the time of the ball milling is 16~24h；The temperature of the drying be 60~80 DEG C, the drying when Between be 8~12h；The screen number of the sieving is 60~120 mesh；The temperature of the pre-burning is 850~950 DEG C, the pre-burning Time be 1~3h；In the step (2), the average grain diameter of the barium titanate is 10~100nm；The medium of the ball milling is deionized water, institute The time for stating ball milling is 16~24h；The temperature of the drying is 100~120 DEG C, and the time of the drying is 8~12h；It is described The screen number of sieving is 60~120 mesh；The temperature of the pre-burning is 950~1100 DEG C, and the time of the pre-burning is 2~8h.
- A kind of 5. anti-reduction X9R type ceramic capacitor dielectric materials, it is characterised in that：It includes compound described in claim 1 With secondary doping agent；The secondary doping agent includes MnO2, component A and B component；The component A is Nb2O5And/or Ta2O5；The B component is CeO2、CaZrO3At least one of with MgO；The mass ratio of the secondary doping agent and the compound is 0.5~2.0:100.
- 6. dielectric material according to claim 5, it is characterised in that：The MnO2Mass ratio with the compound is 0.1 ~1.0：100；The component A and the mol ratio of the compound are 1.0~4.0：100；The mass ratio of the B component and the compound is 0.1~2.0：100.
- 7. the dielectric material according to claim 5 or 6, it is characterised in that：The anti-reduction X9R type ceramic capacitor dielectrics Material is made up of the compound and secondary doping agent.
- 8. the preparation method of the dielectric material any one of claim 5-7, comprises the following steps：By the compound and The secondary doping agent mixing and ball milling, drying, sieving, obtain ceramic powder；After the ceramic powder tabletting, Sintered in reducing atmosphere stove, that is, obtain the anti-reduction X9R type ceramic capacitor dielectric materials.
- 9. preparation method according to claim 8, it is characterised in that：The reducing atmosphere of the reducing atmosphere stove is N2/H2；The process of the sintering comprises the following steps：1) 300~400 DEG C are risen to 150~200 DEG C/h heating rate, is incubated 0.5~2h；2) in the reducing atmosphere, humidify simultaneously, partial pressure of oxygen is controlled 10-9~10-13In atm, with 150~200 DEG C/h's Temperature is risen to 1150~1200 DEG C and is sintered by heating rate, and is incubated 1~3 hour；3) partial pressure of oxygen is controlled 10-4~10-5Atm anneals, 800 are cooled the temperature to 200~300 DEG C/h rate of temperature fall~ 1100 DEG C, 2.5~4h is incubated, room temperature is cooled to the reducing atmosphere stove.
- 10. preparation method according to claim 8 or claim 9, it is characterised in that：The medium of the ball milling is deionized water, institute The time for stating ball milling is 16~24h；The temperature of the drying is 100~120 DEG C, and the time of the drying is 6~12h；The screen number of the sieving is 60~120 mesh；In methods described, the tableting processes are by the ceramic powder and organic binder bond mixed pressuring plate；The mass ratio of the ceramic powder and the organic binder bond is 100：1.5~3.0.
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| CN110128132A (en) * | 2019-05-22 | 2019-08-16 | 北京工业大学 | Unleaded medium material for multilayer ceramic capacitors of a kind of ultra-wide temperature fine grain height Jie and preparation method thereof |
| CN110304916A (en) * | 2019-04-25 | 2019-10-08 | 武汉理工大学 | A kind of anti-reduction BaTiO3Base media ceramic and preparation method |
| CN112939597A (en) * | 2021-04-06 | 2021-06-11 | 上海大学 | PTCR thermal sensitive ceramic material and preparation method thereof |
| CN113307622A (en) * | 2021-07-07 | 2021-08-27 | 天津大学 | High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof |
| CN113666738A (en) * | 2021-08-31 | 2021-11-19 | 华南理工大学 | Barium titanate-based X9R dielectric material for multilayer ceramic capacitor and preparation method thereof |
| CN114031394A (en) * | 2021-10-22 | 2022-02-11 | 江苏钧瓷科技有限公司 | Method for improving reduction resistance of PTCR (thermal sensitive ceramic) |
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| CN102199035A (en) * | 2011-03-22 | 2011-09-28 | 清华大学 | X9r ceramic capacitor dielectric material and preparation method thereof |
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| CN110128132A (en) * | 2019-05-22 | 2019-08-16 | 北京工业大学 | Unleaded medium material for multilayer ceramic capacitors of a kind of ultra-wide temperature fine grain height Jie and preparation method thereof |
| CN112939597A (en) * | 2021-04-06 | 2021-06-11 | 上海大学 | PTCR thermal sensitive ceramic material and preparation method thereof |
| CN113307622A (en) * | 2021-07-07 | 2021-08-27 | 天津大学 | High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof |
| CN113307622B (en) * | 2021-07-07 | 2023-03-10 | 天津大学 | High-performance reduction-resistant barium titanate-based dielectric ceramic and preparation method thereof |
| CN113666738A (en) * | 2021-08-31 | 2021-11-19 | 华南理工大学 | Barium titanate-based X9R dielectric material for multilayer ceramic capacitor and preparation method thereof |
| CN114031394A (en) * | 2021-10-22 | 2022-02-11 | 江苏钧瓷科技有限公司 | Method for improving reduction resistance of PTCR (thermal sensitive ceramic) |
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